JP2021512179A - A cross-linking agent compound, a photosensitive composition containing the same, and a photosensitive material using the same. - Google Patents

Abstract

The present invention relates to a cross-linking agent compound in which a terminal cross-linking functional group is capped with a silane-based protecting group, a photosensitive composition containing the same, and a photosensitive material using the same.

Description

[Cross-reference of related applications]
This application claims the benefit of priority under Korean Patent Application No. 10-2018-0167760 dated December 21, 2018, and all the contents disclosed in the literature of the Korean patent application are part of this specification. Included as a part.

The present invention relates to a cross-linking agent compound having excellent cross-linking property and improved solubility in a solvent, a photosensitive composition capable of realizing excellent mechanical strength and storage stability during synthesis of a photosensitive material, and a photosensitive material using the same.

The photosensitive resin is a typical functional polymer material that has been put into practical use in the production of various precision electronic and information industry products, and is currently importantly used in the advanced technology industry, especially in the production of semiconductors and displays. ..

In general, a photosensitive resin means a polymer compound in which a chemical change in molecular structure occurs in a short time by light irradiation, and physical properties such as solubility, coloring, and curing in a specific solvent change. Fine precision processing is possible by using photosensitive resin, energy and raw materials can be greatly reduced compared to the thermal reaction process, work can be performed quickly and accurately in a small installation space, and tip printing. It is widely used in various precision electronics and information industries such as fields, semiconductor production, display production, and photo-curing surface coating materials.

On the other hand, recently, there is a demand for a photosensitive resin capable of minimizing the defect rate and increasing the processing efficiency and the resolution while the electronic device is highly integrated and finely patterned. This introduces a method of using a polyamic acid, a polyamic acid, or the like as a photosensitive resin.

However, polyamic acid is easily hydrolyzed by moisture in the air and has insufficient storage stability and stability, and polyamic acid has low adhesion to the substrate to which it is applied. There was a problem of deteriorating the physical properties of the substrate. In particular, the photosensitive resin has a problem that the mechanical properties in the finally cured state are not sufficient.

Therefore, in order to produce a photosensitive material having high mechanical properties required in the display field, a method of adding various cross-linking agents to the photosensitive composition has been proposed, but the solubility of the cross-linking agent compound is not sufficient. There was a limit to the decrease in stability and dispersibility, the inability of the photosensitive composition to have uniformity, and the decrease in reliability.

Therefore, it is required to develop a cross-linking agent compound which is excellent in cross-linking property and can realize excellent mechanical properties, and can have improved solubility and excellent storage stability and dispersibility in the composition. There is.

The present invention provides a cross-linking agent compound having excellent cross-linking property and improved solubility in a solvent.

The present invention also provides a photosensitive composition capable of achieving excellent mechanical strength and storage stability during the synthesis of photosensitive materials.

The present invention also provides a photosensitive material using the photosensitive composition.

上記化学式１中、Ａは、１価〜４価の芳香族官能基であり、ｊは、１〜４の整数であり、Ｌ_１およびＬ_２は、それぞれ独立して、炭素数１〜１０のアルキレン基または炭素数６〜２０のアリーレン基のうちの一つであり、Ｒ_１およびＲ_２は、それぞれ独立して、ケイ素含有一価官能基である。 The present invention provides a cross-linking agent compound represented by the following chemical formula 1.
[Chemical formula 1]

In the above chemical formula 1, A is a monovalent to tetravalent aromatic functional group, j is an integer of 1 to 4, and L ₁ and L ₂ are independently having 1 to 10 carbon atoms. It is one of an alkylene group or an arylene group having 6 to 20 carbon atoms, and R ₁ and R ₂ are independently silicon-containing monovalent functional groups.

The present invention also provides a photosensitive composition containing the cross-linking agent compound.

The present invention also provides a photosensitive composition containing the cross-linking agent compound and a polymer containing at least one or more carboxyl groups.

The present invention also provides a photosensitive material containing a cured product of the photosensitive composition.

Hereinafter, a cross-linking agent compound according to a specific embodiment of the present invention, a photosensitive composition containing the same, and a photosensitive material using the same will be described in more detail.

Unless otherwise specified herein, the following terms are defined as follows:

As used herein, if a component is'included'in a component, it may include other components further, rather than excluding other components, unless otherwise stated otherwise. Means.

As used herein, the term'substitution'means that another functional group is attached in place of the hydrogen atom in the compound, and the position to be substituted is the position where the hydrogen atom is substituted, that is, the substituent is. The position is not limited as long as it can be substituted, and when two or more substituents are substituted, the two or more substituents may be the same or different from each other.

As used herein, the term'substituted or unsubstituted' refers to heavy hydrogen; halogen group; cyano group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amide group; amino group; carboxy group; sulfone. Acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkylthioxy group; arylthioxy group; alkylsulfoxi group; arylsulfoxi group; silyl group; boron group; alkyl group; cycloalkyl group; Alkenyl group; aryl group; aralkyl group; aralkenyl group; alkylaryl group; arylphosphin group; or one or more selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms. It means substituted or unsubstituted with a substituent, or substituted or unsubstituted in which two or more substituents among the above-exemplified substituents are linked. For example, the'substituent in which two or more substituents are linked'may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are linked.

In the present specification, the (co) polymer means a polymer or a copolymer including all of them, the polymer means a homopolymer composed of a single repeating unit, and the copolymer means 2 It means a copolymer containing a repeating unit of more than one species.

In the present specification, the (co) polymer is used in the sense of including all random (co) polymers, block (co) polymers, graft (co) polymers and the like.

は、他の置換基に連結される結合を意味し、直接結合は、Ｌで表示される部分に他の原子が存在しないことを意味する。 In the present specification

Means a bond linked to another substituent, and a direct bond means that no other atom is present in the portion represented by L.

In the present specification, the alkyl group is a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 10. According to other embodiments, the alkyl group has 1 to 6 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, Pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , N-Heptyl, 1-methylhexyl, Cyclopentylmethyl, Cycloheptylmethyl, Octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

As used herein, the alkylene group is a divalent functional group derived from an alkane and has 1 to 20, or 1 to 10, or 1 to 5 carbon atoms. For example, it is linear, branched or cyclic and can be a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group, a hexylene group or the like. One or more hydrogen atoms contained in the alkylene group can be substituted with the same substituents as in the case of the alkyl group.

In the present specification, the aryl group is a monovalent functional group derived from arene, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and is a monocyclic aryl group or a polycyclic group. It may be an aryl group. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, or the like, but is not limited thereto. The polycyclic aryl group may be, but is not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a peryleneyl group, a chrysenyl group, a fluorenyl group and the like. The aryl group may be substituted or unsubstituted.

In the present specification, the arylene group is a divalent functional group derived from arene, which may be monocyclic or polycyclic, and has 6 to 20 or 6 to 10 carbon atoms. is there. For example, it may be a phenylene group, a biphenylene group, a terphenylene group, a stillbenylene group, a naphthylenel group, or the like, but is not limited thereto. One or more hydrogen atoms contained in the arylene group can be substituted with the same substituents as in the case of the alkyl group.

As used herein, a polyvalent functional group is a residue in which a plurality of hydrogen atoms bonded to an arbitrary compound have been removed, and is, for example, a divalent functional group, a trivalent functional group, or a tetravalent functional group. Functional groups can be mentioned. As an example, a tetravalent functional group derived from cyclobutane means a residue in the form in which any four hydrogen atoms attached to cyclobutane have been removed.

As used herein, a direct bond or a single bond means that no atom or group of atoms is present at that position and is connected by a bond line. _{Specifically, it means that no other atom exists in the portion represented by Ra} or L _b (a and b are integers of 1 to 20, respectively) in the chemical formula.

In the present specification, the weight average molecular weight means the polystyrene-equivalent weight average molecular weight measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analyzer, a detector such as a differential refractive index detector, and a column for analysis can be used, and are usually applied. The temperature conditions, solvent, and flow rate to be applied can be applied. As a specific example of the measurement conditions, a Polystyrene Laboratories PLgel MIX-B 300 mm long column is used, a Waters PL-GPC220 instrument is used, the evaluation temperature is 160 ° C., and 1,2,4-trichlorobenzene is used. Was used as a solvent, the flow rate was 1 mL / min, the sample was prepared to a concentration of 10 mg / 10 mL, then supplied in an amount of 200 μL, and the Mw value was determined using a calibration curve formed using a polystyrene standard. Can be sought. The molecular weight of polystyrene standard products is 9 of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000. Seeds were used.

As the cross-linking agent compound according to the present invention is represented by the above chemical formula 1, the present inventors end the hydroxy group (-OH), which is a cross-linking functional group, with a specific functional group of _{R 1} and R _2. When substituted, _{the functional groups of R 1} and R ₂ act as protective groups to increase the solubility and dispersibility of the cross-linking agent compound, and the cross-linking agent compound becomes uniform in the composition to which the cross-linking agent compound is added. By dispersing, it was confirmed through experiments that it had an excellent cross-linking effect, and the invention was completed.

Further, when the terminal of the hydroxy group (-OH) which is the crosslinkable _{functional group is replaced with the silicon-containing functional group of R 1} and R ₂ , the present inventors include the existing hydroxy by containing the silicon-containing functional group. It was confirmed that the reactivity of the cross-linking agent in the initial drying step was lower than that of the cross-linking agent at the terminal (-OH), and the cross-linking reaction was started after the heat treatment to reduce the deterioration of the initial physical properties due to the cross-linking agent.

_{The functional groups of R 1} and R ₂ introduced into the terminal of the cross-linking functional group of the cross-linking agent compound suppress the cross-linking reaction by the cross-linking functional group in the photosensitive composition and minimize the formation of an unnecessary cross-linking structure. The stability and reliability of the composition can be improved, and the hydroxy group at the end of the crosslinkable functional group recovers smoothly while being attached and detached and removed at a temperature of about 80 ° C. or higher by heat treatment during the synthesis of the photosensitive material. The cross-linking reaction can be carried out to improve the mechanical properties of the photosensitive material.

That is, in the photosensitive composition, the structure of the cross-linking agent compound represented by the above chemical formula 1 is maintained, and the polymer containing at least one or more carboxyl groups and the cross-linking agent compound represented by the above chemical formula 1 are crosslinked. The reaction can be suppressed. Further, the functional groups _{of R 1} and R ₂ are contained in the cross-linking agent compound represented by the above chemical formula 1 when the temperature rises due to heat treatment through a drying step, an exposure step, a curing step, etc. for producing a photosensitive material from the photosensitive composition. The cross-linking reaction between the polymer containing at least one or more carboxyl groups and the cross-linking agent compound represented by the chemical formula 6 described later can proceed while being substituted with a hydrogen atom.

Therefore, the photosensitive composition of the above embodiment suppresses the cross-linking reactivity of the cross-linking agent compound added to the composition to improve the dispersibility of the cross-linking agent compound and the polymer containing at least one carboxyl group. The strength of the photosensitive material can be sufficiently improved and the strength of the photosensitive material is increased through an interpolymer cross-linking reaction containing a cross-linking agent compound and at least one carboxyl group in the composition during the production process of the photosensitive material of another embodiment described later. The effect of improving can be realized.

1. 1. Crosslinking agent compound The crosslinking agent compound according to the present invention can have a specific chemical structure represented by the above chemical formula 1. The physical / chemical properties of the cross-linking agent compound are considered to be due to the specific structure of Chemical Formula 1 described above.

In the above chemical formula 1, A is a monovalent to tetravalent aromatic functional group, and j is an integer of 1 to 4. A is an aromatic functional group located at the center of the cross-linking agent compound, and about j functional groups represented by curly braces'[]' in Chemical Formula 1 are bonded to the terminal functional group contained in A. can do.

That is, if j is 1 in the above chemical formula 1, A is a monovalent functional group. If j is 2, A is a divalent functional group. If j is 3, A is a trivalent functional group. If j is 4, A is a tetravalent functional group.

Preferably, in the above chemical formula 1, A is an arylene group having 6 to 30 carbon atoms, and j is 2.

When the functional group located at the center of the cross-linking agent compound represented by A is an aromatic functional group like the cross-linking agent compound represented by the chemical formula 1, the cross-linking agent compound in which the aliphatic functional group is located at the center Compared with this, heat resistance and dimensional stability can be improved. This is because the inclusion of aromatic functional groups increases intermolecular attractive force and rigidity.

上記化学式２中、Ｌ_３は、単一結合、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＣＯＯ−、−（ＣＨ_２）ｚ−、−Ｏ（ＣＨ_２）_ｚＯ−、−Ｏ（ＣＨ_２）_ｚ−、−ＯＣＨ_２−Ｃ（ＣＨ_３）_２−ＣＨ_２Ｏ−、−ＣＯＯ−（ＣＨ_２）_ｚ−ＯＣＯ−、または−ＯＣＯ−（ＣＨ_２）_ｚ−ＣＯＯ−であり、ｚは、それぞれ独立して、１〜１０の整数であり、ｋは１〜３の整数であり、ｎおよびｍは、それぞれ独立して、０〜３の整数である。 More specifically, in the above chemical formula 1, A is a divalent aromatic functional group represented by the following chemical formula 2, and j is 2.
[Chemical formula 2]

In the above chemical formula 2, L ₃ is a single bond, -O-, -CO-, -S-, -SO _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -COO. -,-(CH ₂ ) z-, -O (CH ₂ ) _z O-, -O (CH ₂ ) _z- , -OCH _2- C (CH ₃ ) _2- CH ₂ O-, -COO- (CH) ₂ ) _z- OCO- or -OCO- (CH ₂ ) _z- COO-, where z is an integer of 1-10 independently, k is an integer of 1-3, n and m is an integer of 0 to 3 independently of each other.

In the above chemical formula 1, L ₁ and L ₂ are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and L ₁ and L _{2 are preferable.} May be independently alkylene groups having 1 to 5 carbon atoms, for example, ethylene groups.

In the above chemical formula 1, R ₁ and R ₂ are functional groups in which the hydroxy group (-OH) terminal, which is a cross-linking functional group of the cross-linking agent compound, is substituted instead of a hydrogen atom, and at least one or more. It is possible to suppress the cross-linking reaction between the polymer containing a carboxyl group and the cross-linking agent compound represented by the above chemical formula 1.

As will be described later, _{the functional groups of R 1} and R ₂ are hydrogen atoms when the temperature rises to about 80 ° C. or higher through a drying step, an exposure step, a curing step, etc. for producing a photosensitive material from a photosensitive composition. It can be replaced with and attached / detached.

The R ₁ and R ₂ may be independently silicon-containing monovalent functional groups.

上記化学式３中、Ｒ_５〜Ｒ_７は、それぞれ独立して、水素、または炭素数１〜１０のアルキル基のうちの一つであってもよい。 Specifically, the silicon-containing monovalent functional group may be a functional group represented by the following chemical formula 3.
[Chemical formula 3]

In the above chemical formula 3, R _{5 to} R ₇ may be independently one of hydrogen or an alkyl group having 1 to 10 carbon atoms.

More specifically, in the above chemical formula 3, R _{5 to} R ₇ may be an alkyl having 1 to 10 carbon atoms, preferably a methyl group or an ethyl group.

上記化学式１−１中、Ａ'は、２価の芳香族官能基であり、Ｌ_４〜Ｌ_７は、それぞれ独立して、炭素数１〜１０のアルキレン基または炭素数６〜２０のアリーレン基のうちの一つであり、Ｒ_３、Ｒ_３'、Ｒ_４、およびＲ_４'は、それぞれ独立して、ケイ素含有一価官能基である。 In the above chemical formula 1, A is a divalent aromatic functional group and n is 2. That is, the cross-linking agent compound represented by the above chemical formula 1 can include a compound represented by the following chemical formula 1-1.
[Chemical formula 1-1]

In the above chemical formula 1-1, A'is a _{divalent aromatic functional group, and L 4 to L 7} are independently alkylene groups having 1 to 10 carbon atoms or arylene groups having 6 to 20 carbon atoms. is one _{of, R 3, R 3 ',} R 4, and _{R 4'} are each independently a silicon-containing monovalent functional group.

Specifically, in the above chemical formula 1-1, A'may be an arylene group having 6 to 30 carbon atoms, and more specifically, a divalent aromatic functional group represented by the above chemical formula 2.

Further, in the above chemical formula 1-1, L _{4 to} L ₇ are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and are R ₃ and R. ₃ ', R _4, and R _4' are each independently, may be a silicon-containing monovalent functional group.

More specifically, as an example of the cross-linking agent compound represented by the above chemical formula 1-1, A'is a divalent aromatic functional group represented by the above chemical formula 2, and L _{4 to} L ₇ are. all an ethylene group having 2 carbon _atoms, R 3 to R _6, all functional group represented by formula _{3 (R 3, R 3 '} , R 4, and _{R 4'} is a methyl group), Examples thereof include compounds represented by the following chemical formula 1-2.
[Chemical formula 1-2]

Further, as another example of the cross-linking agent compound represented by the above chemical formula 1-1, A'is a divalent aromatic functional group represented by the above chemical formula 2, and L _{4 to} L ₇ are all. an ethylene group having 2 carbon _atoms, R 3 to R _6, all functional group represented by formula _{3 (R 3, R 3 '} , R 4, and _{R 4'} are ethyl group), the following chemical formula Examples thereof include compounds represented by 1-3.
[Chemical formula 1-3]

On the other hand, the cross-linking agent compound represented by the above chemical formula 1 is excellent in solubility in a solvent, and the mixed solution to be mixed for 10 seconds after adding the cross-linking agent compound to the solvent can be transparent.

The mixed solution is a mixture of the cross-linking agent compound represented by the above chemical formula 1 and a solvent. Examples of the solvent are not particularly limited, and examples of the solvent contained in the photosensitive composition include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam. , 2-Pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfoxide, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy -N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethylamyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone , Ethylene carbonate, propylene carbonate, jiglime, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether , Ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate and the like. These may be used alone or in combination.

In the mixed solution, the cross-linking agent compound represented by the chemical formula 1 is 1% by weight to 30% by weight, or 2% by weight to 25% by weight, or 10% by weight to 25% by weight based on the total weight of the mixed solution. %, Or 10% by weight and 25% by weight or less.

On the other hand, according to one embodiment of the present invention, the cross-linking agent compound represented by the above chemical formula 1 can be used for photosensitive material applications.

Specifically, the cross-linking agent compound represented by the above chemical formula 1 is a photoresist, an alignment film, an adhesive, an insulating layer, a color filter of a display device, a black matrix of a display device, a column spacer of a display device, and a photocurable property. It can be used in the production of paints, photocurable inks and the like.

As described above, the cross-linking agent compound represented by the above chemical formula 1 has excellent solubility, and when the functional group introduced at the terminal is heat-treated at a temperature of 80 ° C. or higher, the cross-linking functional group terminal is detached and removed while being attached and detached. The hydroxy group of the above can be recovered and a smooth cross-linking reaction can proceed, and such characteristics of the cross-linking agent compound of the present invention can be realized by having a specific structure represented by the above chemical formula 1.

Due to these characteristics, when the cross-linking agent compound represented by the above chemical formula 1 is used as a photosensitive material, the cross-linking agent compound is uniformly dispersed in the photosensitive composition, and the photosensitive material produced from the cross-linking agent compound is uniformly dispersed. Physical properties can be made uniform.

Further, in the process of manufacturing the photosensitive material, the cross-linking reactivity is suppressed at room temperature to sufficiently improve the dispersibility of the cross-linking agent compound and the polymer containing at least one or more carboxyl groups, and at the same time, the photosensitive material is manufactured. By raising the temperature to 80 ° C. or higher through a drying step, an exposure step, a curing step, etc., the hydroxy group at the terminal of the crosslinkable functional group is recovered and the interpolymer crosslinking reaction containing at least one or more carboxyl groups is carried out. By advancing, it is possible to realize a photosensitive material having improved mechanical strength.

Conventional cross-linking agent compounds have technical limitations such as low solubility, reduced stability and dispersibility of the cross-linking agent, and non-uniformity of the photosensitive composition, resulting in reduced reliability. The cross-linking agent compound of the above chemical formula 1 provided by the invention is not only excellent in solubility, but also has excellent mechanical strength due to the fact that the introduced functional group at the terminal protects the cross-linking hydroxy group. , Can have excellent storage stability and solubility.

2. Photosensitive composition On the other hand, according to one embodiment of the present invention, a photosensitive composition containing a cross-linking agent compound represented by the above chemical formula 1 can be provided.

Further, according to one embodiment of the present invention, a photosensitive composition containing a cross-linking agent compound represented by the above chemical formula 1 and a polymer containing at least one or more carboxyl groups can be provided.

The polymer containing at least one or more carboxyl groups is not particularly limited, and may be, for example, a polymer such as polyamic acid.

The cross-linking agent compound represented by the above chemical formula 1 is 1% by weight to 30% by weight, or 2% by weight to 25% by weight, or 10% by weight to 25% by weight, or 10% by weight, based on the total weight of the photosensitive composition. May be over 25% by weight and up to 25% by weight.

If the content of the cross-linking agent compound is too large, the degree of cross-linking of the polymer containing at least one or more carboxyl groups increases too much, so that the flexibility of the polymer can be reduced, and the composition can be composed. The coatability to a substrate can be reduced by a decrease in storage stability due to an increase in viscosity, a decrease in the dispersibility of a cross-linking agent in the composition, or a gelation reaction in the composition.

On the other hand, if the content of the cross-linking agent compound is too small, the effect of improving the mechanical strength by increasing the degree of cross-linking of the polymer containing at least one or more carboxyl groups may not be sufficiently realized.

When the cross-linking agent compound represented by the above chemical formula 1 is heat-treated at a temperature above a certain level, specifically, at a temperature of 80 ° C. or higher, the hydroxy groups are removed while the functional groups of _{R 1} and R _{2 are attached and detached.} The cross-linking functional group terminal of the (OH group) is restored, and a smooth cross-linking reaction can occur with the polymer containing at least one or more carboxyl groups.

However, under normal temperature and pressure conditions of less than 80 ° C., _{a cross-linking agent compound in which some or all of the functional groups of R 1} and R ₂ are substituted with hydrogen atoms and at least two or more terminal cross-linking functional groups are exposed. May be included in part.

This is due to the polymer containing at least one or more carboxyl groups contained in the photosensitive composition of the above embodiment. Specifically, by including the polymer containing at least one or more carboxyl groups, the photosensitive composition exhibits acidic conditions in which the functional groups of _{R 1} and R ₂ are easily attached and detached, and the _{R 1 and} A cross-linking agent compound in which some or all of the functional groups of R ₂ are substituted with hydrogen atoms and at least two or more terminal cross-linking functional groups are exposed may be contained.

That is, the photosensitive composition according to the above embodiment can further contain a cross-linking agent compound in which at least two or more terminal cross-linking functional groups are exposed.

Specifically, the cross-linking agent compound in which at least two or more terminal cross-linking functional groups are exposed may be a cross-linking agent compound represented by the following chemical formula 4.
[Chemical formula 4]

In the above chemical formula 4, A'' is a monovalent to tetravalent functional group, a is an integer of 1 to 4, b is an integer of 0 to 3, and the sum of a and b is 1 to 4. Yes, L _{8 to L 11} are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and at least one of _{R 21} and R _{22 is.} It is hydrogen, the rest is a silicon-containing monovalent functional group, and R ₂₃ and R ₂₄ are independently silicon-containing monovalent functional groups.

More specifically, when R ₂₁ and R ₂₂ are all hydrogen in the above chemical formula 4, a is 1 to 4, one of R ₂₃ and R _{24 in} the above chemical formula 4 is hydrogen, and the rest. Is a silicon-containing monovalent functional group, where a is 2-4.

By including the cross-linking agent compound in which at least two or more terminal cross-linking functional groups are exposed, the photosensitive composition according to the above embodiment is subjected to at least two or more terminal cross-linking with the polymer containing at least one or more carboxyl groups. It can include cross-linking conjugates with cross-linking agent compounds with exposed functional groups.

On the other hand, in the photosensitive composition according to the above embodiment, 0.001 part by weight to 10 parts by weight of the cross-linking agent compound represented by the above-mentioned chemical formula 4 is used with respect to 100 parts by weight of the cross-linking agent compound represented by the above-mentioned chemical formula 1. It can include 0.1 parts by weight to 10 parts by weight, 0.1 parts by weight to 5 parts by weight, or 0.1 parts by weight to 3 parts by weight.

When the photosensitive composition of the above embodiment contains a cross-linking agent compound represented by the above chemical formula 4 so as to satisfy such a range, a cross-linking reaction with a polymer containing at least one or more carboxyl groups. A cross-linking agent compound in which at least two or more terminal cross-linking functional groups are exposed is contained in the photosensitive composition in a small amount, and the photosensitive composition is produced from the photosensitive composition by improving long-term storage stability and reliability. Not only can the physical properties of the material be improved, but also the effect of significantly improving the efficiency of the film forming process can be realized.

On the other hand, when the photosensitive composition contains the cross-linking agent compound represented by the above chemical formula 4 so as to be outside the above-mentioned range, the cross-linking agent compound in which at least two or more terminal cross-linking functional groups are exposed is photosensitive during long-term storage. A large amount is contained in the composition, and a cross-linking reaction occurs between the polymer containing at least one carboxyl group and the cross-linking agent compound in which at least two or more terminal cross-linking functional groups are exposed, and a large number of by-products are formed. , The storage stability of the photosensitive material produced from it is reduced, which makes it unsuitable for long-term storage.

On the other hand, the photosensitive composition can further contain a compound represented by the following chemical formula 5.
[Chemical formula 5]

In the above chemical formula 5, R _{5 to} R ₇ are as defined in the above chemical formula 3.

The compound represented by the chemical formula 5 may be the result of a substitution reaction of the cross-linking agent compound represented by the chemical formula 1.

Specifically, the functional group of R ₁ and R ₂ in the crosslinking compound represented by Formula 1 can detachably all or part of the functional groups R ₁ and R ₂ by substitution reaction, thereby, the It is possible to form a cross-linking agent compound in which at least two or more terminal cross-linking functional groups are exposed and a compound represented by the above chemical formula 5.

On the other hand, the polymer containing at least one or more carboxyl groups can contain a polyamic acid (co) polymer.

[化学式７]

上記化学式６〜７中、Ｘ_３およびＸ_６は、それぞれ独立して、下記化学式８で表される４価の有機基であり、
[化学式８]

上記化学式８中、Ｒ_１３〜Ｒ_１８は、それぞれ独立して、水素または炭素数１〜６のアルキル基であり、Ｌ'は、単一結合、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＲ_１９Ｒ_２０−、−（ＣＨ_２）_Ｚ−、−Ｏ（ＣＨ_２）_ＺＯ−、−ＣＯＯ（ＣＨ_２）_ＺＯＣＯ−、−ＣＯＮＨ−、またはフェニレンの中から選択されるいずれか一つであり、Ｒ_１９およびＲ_２０は、それぞれ独立して、水素、炭素数１〜１０のアルキル基または炭素数１〜１０のハロアルキル基であり、ｚは１〜１０の整数であり、Ｙ_３は、下記化学式９で表される２価の有機基であり、
[化学式９]

上記化学式９中、Ｔは、上記化学式８で表される４価の有機基であり、Ｄ_１およびＤ_２は、それぞれ独立して、炭素数１〜２０のアルキレン基、炭素数１〜１０のヘテロアルキレン基、炭素数３〜２０のシクロアルキレン基、炭素数６〜２０のアリーレン基または炭素数２〜２０のヘテロアリーレン基の中から選択されるいずれか一つであり、Ｙ_６は、下記化学式１０で表される２価の有機基であり、
[化学式１０]

上記化学式１０中、Ａ'は、１５族元素であり、Ｒ'は、水素、または炭素数１〜１０のアルキルであり、ａは、１〜３の整数であり、Ｚ_１〜Ｚ_４のうち少なくとも一つは窒素であり、残りは炭素である。 Specifically, the polymer containing at least one or more carboxyl groups is a first polyamic acid (co) polymer containing a repeating unit represented by the following chemical formula 6, and a repeating unit represented by the following chemical formula 7. A second polyamic acid (co) polymer containing the above can be included.
[Chemical formula 6]

[Chemical formula 7]

Among the chemical formula 6 to 7, X ₃ and X ₆ are each independently a tetravalent organic group represented by the following Chemical Formula 8,
[Chemical formula 8]

In the above chemical formula 8, R _{13 to} R ₁₈ are each independently an alkyl group having hydrogen or 1 to 6 carbon atoms, and L'is a single bond, −O−, −CO−, −COO−, respectively. _{-S -, - SO -, -} SO 2 -, - CR 19 R 20 -, - (CH 2) Z -, - O (CH 2) Z O -, - COO (CH 2) Z OCO -, - CONH -Or one selected from phenylene, R ₁₉ and R ₂₀ are independently hydrogen, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms. , Z is an integer of 1 to 10, and Y ₃ is a divalent organic group represented by the following chemical formula 9.
[Chemical formula 9]

In the chemical formula 9, T is a tetravalent organic group represented by the chemical formula 8, and D ₁ and D ₂ are independently alkylene groups having 1 to 20 carbon atoms and 1 to 10 carbon atoms, respectively. heteroalkylene group, a cycloalkylene group having 3 to 20 carbon atoms, any one selected from among heteroarylene group arylene or C2-20 C6-20, Y ₆ is below It is a divalent organic group represented by the chemical formula 10.
[Chemical formula 10]

In the above chemical formula 10, A'is a group 15 element, R'is hydrogen or an alkyl having 1 to 10 carbon atoms, a is an integer of 1 to 3, and is among _{Z 1 to} Z _4. At least one is nitrogen and the rest is carbon.

[化学式１３]

上記化学式１２〜１３中、Ｒ_９およびＲ_１０のうち少なくとも一つは炭素数１〜１０のアルキル基であり、残りは水素であり、Ｘ_１〜Ｘ_２は、それぞれ独立して、上記化学式８で表される４価の有機基であり、Ｙ_１〜Ｙ_２は、それぞれ独立して、上記化学式９で表される２価の有機基である。 Further, the first polyamic acid (co) polymer which is a polymer containing at least one or more carboxyl groups and contains a repeating unit represented by the above chemical formula 6 is a repeating unit represented by the following chemical formula 12 and the following chemical formula. It may further include one or more repeating units selected from the group consisting of the repeating units represented by 13.
[Chemical formula 12]

[Chemical formula 13]

In the above chemical formulas 12 to 13, _{at least one of R 9} and R ₁₀ is an alkyl group having 1 to 10 carbon atoms, the rest is hydrogen, and X _{1 to} X ₂ are independently of the above chemical formula 8 It is a tetravalent organic group represented by, and Y _{1 to Y 2} are independently divalent organic groups represented by the above chemical formula 9.

That is, the first polyamic acid (co) polymer is represented by the above chemical formula 12 in addition to the homopolymer composed of a single repeating unit represented by the above chemical formula 6 or the repeating unit represented by the above chemical formula 6. It may be a copolymer which is a composite polymer further containing one or more kinds of repeating units selected from the group consisting of a repeating unit to be carried over and a repeating unit represented by the above chemical formula 13.

[化学式１５]

上記化学式１４〜１５中、Ｒ_１１およびＲ_１２のうち少なくとも一つは、炭素数１〜１０のアルキル基であり、残りは水素であり、Ｘ_４〜Ｘ_５は、それぞれ独立して、上記化学式８で表される４価の有機基であり、Ｙ_４〜Ｙ_５は、それぞれ独立して、上記化学式１０で表される２価の有機基である。 The second polyamic acid (co) polymer, which is a polymer containing at least one or more carboxyl groups and contains a repeating unit represented by the above chemical formula 7, has the repeating unit represented by the following chemical formula 14 and the following chemical formula. It may further include one or more repeating units selected from the group consisting of repeating units represented by 15.
[Chemical formula 14]

[Chemical formula 15]

In the above chemical formulas 14 to 15, _{at least one of R 11} and R ₁₂ is an alkyl group having 1 to 10 carbon atoms, the rest is hydrogen, and X _{4 to} X ₅ are independent of the above chemical formulas. It is a tetravalent organic group represented by 8, and Y _{4 to Y 5} are independently divalent organic groups represented by the above chemical formula 10.

That is, the second polyamic acid (co) polymer is represented by the above chemical formula 14 in addition to the homopolymer composed of a single repeating unit represented by the above chemical formula 7 or the repeating unit represented by the above chemical formula 7. It may be a copolymer which is a composite polymer further containing one or more kinds of repeating units selected from the group consisting of a repeating unit to be carried over and a repeating unit represented by the above chemical formula 15.

Specifically, the first polyamic acid (co) polymer always contains the repeating unit represented by the above chemical formula 6, and the repeating unit represented by the above chemical formula 12 and the repeating unit represented by the above chemical formula 13. One of them or a combination thereof can be further included.

Specifically, the second polyamic acid (co) polymer always contains the repeating unit represented by the above chemical formula 7, and the repeating unit represented by the above chemical formula 14 and the repeating unit represented by the above chemical formula 15. One of them or a combination thereof can be further included.

In the first polyamic acid (co) polymer and the second polyamic acid (co) polymer in the photosensitive composition according to the above embodiment, X _{1 to} X ₆ are independently represented by the above chemical formula 8. It may be a tetravalent organic group. The X _{1 to} X ₆ may be a functional group derived from a polyamic acid, a polyamic acid ester, or a tetracarboxylic dianhydride compound used in the synthesis of polyimide.

In the above chemical formula 8, R _{13 to} R ₁₈ are each independently an alkyl group having hydrogen or 1 to 6 carbon atoms, and L'is a single bond, −O−, −CO−, −COO−, respectively. _{-S -, - SO -, -} SO 2 -, - CR 19 R 20 -, - (CH 2) Z -, - O (CH 2) Z O -, - COO (CH 2) Z OCO -, - CONH -Or one selected from phenylene, and R _{19 and R 20} in the L'are independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, respectively. Is a haloalkyl group of, and z in the L'is an integer of 1 to 10.

[化学式８−２]

[化学式８−３]

[化学式８−４]

[化学式８−５]

[化学式８−６]

More preferably, the X _{1 to} X ₆ are independently derived from cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride, which are organic groups of the following chemical formula 8-1, 1,3-dimethyl. Tetrahydro- [3,3'-bifuran] -2,2', 5,5'-tetraone, an organic group of the following chemical formula 8-2 derived from cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride The organic group of the following chemical formula 8-3 derived from, the organic group of the following chemical formula 8-4 derived from 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, the following chemical formula derived from pyromellitic acid dianhydride It may be an organic group of 8-5 or an organic group of the following chemical formula 8-6 derived from 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride.
[Chemical formula 8-1]

[Chemical formula 8-2]

[Chemical formula 8-3]

[Chemical formula 8-4]

[Chemical formula 8-5]

[Chemical formula 8-6]

On the other hand, of the photosensitive composition according to an embodiment, the first polyamic acid (co) polymer is Y ₁ to Y ₃ in the repeating unit of Formula 6 or Formula 12 to 13 are each independently the chemical formula It may be a divalent organic group represented by 9. Since the first polyamic acid (co) polymer is synthesized from a diamine containing an already imidized imide repeating unit, it is immediately irradiated with light after forming a coating film without a high-temperature heat treatment step to generate anisotropy. Since the alignment film can be completed by proceeding with the heat treatment thereafter, not only the light irradiation energy can be significantly reduced, but also the orientation and stability are excellent even in a simple process including one heat treatment step. Not only that, it is possible to produce a photosensitive material having excellent voltage maintenance and maintenance rate and electrical characteristics.

[化学式８−２]

Specifically, in the above chemical formula 9, T may be a functional group represented by the following chemical formula 8-1 or a functional group represented by the following 8-2.
[Chemical formula 8-1]

[Chemical formula 8-2]

[化学式９−２]

More specifically, the example of the organic group represented by the above chemical formula 9 is not particularly limited, but may be, for example, a functional group represented by the following chemical formula 9-1 or chemical formula 9-2. ..
[Chemical formula 9-1]

[Chemical formula 9-2]

In the first polyamic acid (co) polymer, the repeating unit represented by the above chemical formula 6 can be contained in an amount of 5 mol% to 74 mol% or 10 mol% to 60 mol% with respect to the total repeating unit.

As described above, if a polymer containing the imide repeating unit represented by the chemical formula 6 in a specific content is used, the imide repeating unit in which the first polyamic acid (co) polymer has already been imidized is constant. Since it is contained in the content of, it is possible to omit the high-temperature heat treatment step and produce a photosensitive material having excellent stability even if it is immediately irradiated with light.

That is, it is preferable that the repeating unit represented by the above chemical formula 6 is contained in such a content range because a photosensitive polymer having excellent storage stability can be provided.

Further, the repeating unit represented by the chemical formula 12 or the repeating unit represented by the chemical formula 13 may be contained in an appropriate content according to the desired characteristics.

On the other hand, of the photosensitive composition according to an embodiment of the present invention, the second polyamic acid (co) polymer, Y ₄ to Y ₆ in the repeating unit of Formula 7 or Chemical Formula 14 to 15 are each independently , It may be a divalent organic group represented by the above chemical formula 10. The Y ₄ , Y ₅ , and Y ₆ are defined as divalent organic groups represented by the chemical formula 10, and can provide photosensitive polymers having various structures capable of exhibiting the above effects.

In the above chemical formula 10, A'is a group 15 element, and the group 15 element may be nitrogen (N), phosphorus (P), arsenic (As), tin (Sn) or bismuth (Bi). The R'is a functional group bonded to the A, and can be bonded to the A'element as many as the number represented by a. Preferably, in the above chemical formula 10, A'is nitrogen, R'is hydrogen, and a is 1.

On the other hand, in the chemical formula 10, at least one of Z ₁ to Z ₄ is nitrogen, because the condition that the remainder being carbon, the formula 10 by the nitrogen atom, based on the center point or center line May form an asymmetric structure that is not symmetrical. The chemical formula 10 is a repeating unit derived from a diamine having a specific structure containing a nitrogen atom or the like, which is a precursor used for forming a photosensitive polymer, and is considered to be due to the use of an asymmetric diamine described later.

The organic group represented by the chemical formula 10 is a structural feature in which two aromatic ring compounds, preferably a heteroaromatic ring compound and an aromatic ring compound, are bonded to each other via a secondary amine group or a tertiary amine group. Has.

More specifically, in the above chemical formula 10, _{one of Z 1 to} Z ₄ may be nitrogen and the rest may be carbon, or in the above chemical formula 15, _one of Z 1 or Z ₃ may be. Nitrogen, the rest is carbon, and Z ₂ and Z ₄ may be carbon. That is, in the above chemical formula 10, the _{aromatic ring containing Z 1 to} Z ₄ can have a pyridine (pyridine) structure.

[化学式１０−２]

[化学式１０−３]

上記化学式１０−１〜１０−３中、Ａ'、Ｚ_１〜Ｚ_４、Ｒ'、ａに対する内容は、上記化学式１０で上述した内容を含む。 Further, the chemical formula 10 may contain one or more functional groups selected from the group consisting of the following chemical formulas 10-1, 10-2 and 10-3.
[Chemical formula 10-1]

[Chemical formula 10-2]

[Chemical formula 10-3]

Among the chemical formula _{10-1~10-3, A ', Z 1 ~Z} 4, R', content for a includes the contents described above in Formula 10.

[化学式１０−５]

[化学式１０−６]

More specifically, the example of the organic group represented by the above chemical formula 10 is not particularly limited, but is selected from the group consisting of the following chemical formulas 10-4, 10-5 and 10-6, for example. It may be one or more functional groups.
[Chemical formula 10-4]

[Chemical formula 10-5]

[Chemical formula 10-6]

On the other hand, the photosensitive composition according to the embodiment of the present invention has a content of 10 parts by weight to 1,000 parts by weight of the second polyamic acid (co) polymer with respect to 100 parts by weight of the first polyamic acid (co) polymer. It is preferably parts by weight, or 15 parts by weight to 800 parts by weight.

The weight average molecular weight (GPC measurement) of each of the first polyamic acid (co) polymer and the second polyamic acid (co) polymer is not particularly limited, but is, for example, 10,000 g / mol to 200,000 g. It is preferably / mol.

3. 3. Photosensitive material On the other hand, according to still another embodiment of the present invention, a photosensitive material containing a cured product of the photosensitive composition of the above embodiment can be provided. The cured product means a substance obtained through the curing step of the photosensitive composition of the above embodiment.

When the form of the photosensitive material is realized by a film, a film, or the like, the thickness of the photosensitive material is not particularly limited, but can be freely adjusted within the range of, for example, 0.01 μm to 1,000 μm. .. When the thickness of the photosensitive material increases or decreases by a specific value, the physical properties measured from the photosensitive material may also change by a certain value.

On the other hand, in the manufacturing process of the photosensitive material, _{the functional groups of R 1} and R ₂ of the cross-linking agent compound represented by the above chemical formula 1 can be replaced with hydrogen atoms and attached / detached, whereby the cross-linking reaction can proceed. it can.

上記化学式１１中、Ａ、ｊ、Ｌ_１およびＬ_２は、前記一実施形態の化学式１で定義した通りである。 That is, the photosensitive material can include a combination of a cross-linking agent compound represented by the following chemical formula 11 and a polymer containing at least one or more carboxyl groups.
[Chemical formula 11]

In the above chemical formula 11, A, j, L ₁ and L ₂ are as defined in the chemical formula 1 of the above embodiment.

The combination of the cross-linking agent compound represented by the chemical formula 11 and the polymer containing at least one or more carboxyl groups is a hydroxy group (-) which is a cross-linking functional group contained in the cross-linking agent compound represented by the chemical formula 11. OH) is bonded to the carbonyl group (-CO-) of the carboxyl group (-COOH) contained in the polymer containing at least one or more carboxyl groups to form an ester bond (-COO).

When the photosensitive composition of the above embodiment contains a cross-linking agent compound represented by the above chemical formula 11, a part of the cross-linking reaction proceeds in the composition, so that the cross-linking agent compound becomes uniform in the composition. It is difficult to disperse and storage stability is also reduced.

On the other hand, in the present invention, the cross-linking agent compound represented by the above chemical formula 1 is added in the photosensitive composition to suppress the cross-linking reaction in the composition, and the chemical formula 1 is voluntarily used in the manufacturing process of the photosensitive material. The cross-linking agent compound represented can be induced to be converted into the cross-linking agent compound represented by Chemical Formula 11. Thereby, the composition can improve the dispersibility and safety of the cross-linking agent compound, and the photosensitive material can realize the effect of improving the mechanical strength by forming the cross-linked structure.

Specifically, the example of the photosensitive material according to the above embodiment is not particularly limited, and for example, a photoresist, an alignment film, an adhesive, an insulating layer, a color filter of a display device, a black matrix of a display device, and a column of a display device are used. Examples include spacers, photocurable paints, photocurable inks and the like.

According to the present invention, a cross-linking agent compound having excellent solubility and an improved cross-linking effect can have high dispersibility and high reliability, and excellent mechanical strength can be realized at the time of synthesizing a photosensitive material. It is possible to provide a photosensitive composition which can be obtained and has excellent storage stability, and a photosensitive material using the same.

The present invention will be described in more detail with reference to the following examples. However, the following examples merely exemplify the present invention, and the content of the present invention is not limited to the following examples.

<Manufacturing example and comparative manufacturing example>

Production Example 1: Production of cross-linking agent

N4, N4, N4', N4'-tetrakis (2-hydroxyethyl) biphenyl-4,4'-dicarboxyamide (N4, N4, N4', N4'-tetrakis (2-hydroxyethyl) biphenyl- under a nitrogen atmosphere After dispersing 4,4'-dicarboxamide (13.0 g, 31.3 mmol) and triethylamine (19.0 g, 187.8 mmol) in dichloromethane (200 mL), the compound trimethylsilyl chloride (13.5 g, 125.2 mmol) was added. Then, the mixture was stirred at 0 ° C. for 2 hours and at room temperature for 16 hours. After completion of the reaction, a saturated aqueous solution of sodium hydrogen carbonate (300 ml) was added, and the aqueous solution layer was extracted twice with dichloromethane (200 mL). This was treated with magnesium sulfate (10 g) and dried. The filtered filtrate is concentrated to concentrate N4, N4, N4', N4'-tetrakis (2- (trimethylsilyloxy) ethyl) biphenyl-4,4'-dicarboxamide (N4, N4, N4', N4'-tetracis ( 2- (Trimethylsilyloxy) ethyl) biphenyl-4,4'-dicarboxamide, 17.5 g, yield 79.3%) was produced.

MS [M + H] ⁺ = 705

Production Example 2: Production of cross-linking agent

N4, N4, N4', N4'-tetrakis (2- (triethyl)) in the same manner as in Production Example 1 except that chlorotriethylsilane was used instead of chlorotrimethylsilane. Cyriloxy) ethyl) biphenyl-4,4'-dicarboxyamide (N4, N4, N4', N4'-tetrakis (2- (triethylsilyloxy) ethyl) biphenyl-4,4'-dicarboxamide) was produced.

MS [M + H] ⁺ = 872

Comparative Production Example 1: Production of Crosslinking Agent N4, N4, N4', N4'-tetrakis (2-hydroxyethyl) biphenyl-4,4'-dicarboxyamide (N4, N4'), which is the reaction product of Production Example 1. N4', N4'-tetracis (2-hydroxyethyl) biphenyl-4,4'-dicarboxamide) was used as the cross-linking agent of Comparative Production Example 1.

<Example: Production of photosensitive composition and photosensitive material>

<Example>

Example 1: Preparation of photosensitive composition 5.0 g (13.3 mmol) of diamine DA1 represented by the following chemical formula A was completely dissolved in 71.27 g of anhydrous N-methylpyrrolidone (NMP). Then, 2.92 g (13.03 mmol) of 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic dianhydride (DMCBDA) was added to the solution under ice bath, and the temperature was room temperature for about 16 hours. The polymer P-1 was produced by stirring with. As a result of confirming the molecular weight of the polymer P-1 by GPC, the number average molecular weight (Mn) was 15,500 g / mol and the weight average molecular weight (Mw) was 31,000 g / mol. The monomer structure of the polymer P-1 was determined by the equivalent ratio of the monomers used, and the ratio of the imide structure in the molecule was 50.5% and the ratio of the amic acid structure was 49.5%. ..
[Chemical formula A]

19.743 g (0.099 mol) of diamine DA2 represented by the following chemical formula B was completely dissolved in 225.213 g of anhydrous N-methylpyrrolidone (NMP). Then, 20.0 g (0.092 mol) of pyromellitic dianhydride (PMDA) was added to the solution under ice bath, and the mixture was stirred at room temperature for about 16 hours to produce the polymer Q-1. .. As a result of confirming the molecular weight of the polymer Q-1 by GPC, the weight average molecular weight (Mw) was 27,000 g / mol.
[Chemical formula B]

10 g of the polymer P-1 and 10 g of the polymer Q-1 produced as described above were added with 12.4 g of NMP and 7.6 g of n-butoxyethanol (weight ratio 8: 2) to obtain a 5 wt% solution. Then, as a cross-linking agent, 5% by weight of the cross-linking agent obtained in Production Example 1 was added to the solution, and then the mixture was stirred at 25 ° C. for 16 hours. The obtained solution was pressure-filtered with a filter having a pore size of a poly (tetrafluoroethylene) material of 0.1 μm to produce a photosensitive composition.

Example 2: Production of Photosensitive Composition The photosensitive composition is prepared in the same manner as in Example 1 except that the cross-linking agent obtained in Production Example 1 is added in an amount of 10% by weight based on the total solution. Manufactured.

Example 3: Production of Photosensitive Composition By the same method as in Example 1 except that the cross-linking agent obtained in Production Example 2 was added in place of the cross-linking agent obtained in Production Example 1. , A photosensitive composition was produced.

Example 4: Production of Photosensitive Composition The above, except that the cross-linking agent obtained in Production Example 2 was added in an amount of 10% by weight based on the total solution in place of the cross-linking agent obtained in Production Example 1. A photosensitive composition was produced in the same manner as in Example 2.

Comparative Example 1: Production of photosensitive composition N4, N4, N4', N4'-tetrakis (2-hydroxyethyl) biphenyl-4,4 in Comparative Production Example 1 instead of the cross-linking agent obtained in Production Example 1 Photosensitized in the same manner as in Example 1 above, except that'-dicarboxamide (N4, N4, N4', N4'-tetrakis (2-hydroxhyel) biphenyl-4,4'-dicarboxamide) was added. A sex composition was produced.

Table 1 below summarizes the compositions of the photosensitive compositions of the Examples and Comparative Examples.

<Experimental example>

1) Storage stability For the photosensitive compositions produced in the above Examples and Comparative Examples, the initial viscosity and the viscosity after storage at room temperature for 30 days were measured, respectively, and the rate of change in viscosity was measured by the following formula 1. did.

The viscosity of the photosensitive composition was measured by torque with a Brookfield viscometer using a temperature of 25 ° C., a rotation speed of 0.5 rpm and an RV-7 spindle.

[Formula 1]
Viscosity change rate (%) = (Viscosity of photosensitive composition after storage at room temperature for 30 days-Viscosity of initial photosensitive composition) / Viscosity of initial photosensitive composition * 100

The smaller the rate of change in viscosity obtained by the above formula 1, the better the storage stability.

2) Solubility After adding the cross-linking agents used in the photosensitive compositions of the Examples and Comparative Examples to a solvent (γ-butyrolactone) so as to satisfy the addition amount of the cross-linking agent shown in Table 1, 10 A mixed solution mixed for seconds was produced, the transparency of the mixed solution was visually confirmed, and the solubility was evaluated according to the following criteria.

As a result of the measurement, when the mixed solution is transparent, it is evaluated as'excellent', and when the mixed solution is opaque, it is evaluated as'poor', and the results are shown in Table 2 below.

As shown in Table 2 above, in the case of the photosensitive compositions of Examples 1 to 4, the viscosity of the photosensitive composition is changed by using the cross-linking agent compound having a specific structure synthesized in Production Examples 1 and 2. It was confirmed that when the rate was 2.9% or less, excellent storage stability was exhibited and excellent solubility was exhibited.

On the other hand, the photosensitive composition of Comparative Example 1 has very poor storage stability as compared with the above-mentioned Example by using the cross-linking agent compound of Comparative Production Example 1 which does not contain a silicon-containing monovalent functional group. Not only that, it was confirmed that the solubility was also poor.

Claims (14)

Crosslinking agent compound represented by the following chemical formula 1:
[Chemical formula 1]

In the above chemical formula 1,
A is a monovalent to tetravalent aromatic functional group.
j is an integer of 1 to 4 and
L ₁ and L ₂ are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms.
R ₁ and R ₂ are independent silicon-containing monovalent functional groups. In the above chemical formula 1,
A is a divalent aromatic functional group represented by the following chemical formula 2.
The cross-linking agent compound according to claim 1, wherein j is 2.
[Chemical formula 2]

In the above chemical formula 2,
L ₃ is a single bond, -O-, -CO-, -S-, -SO _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -COO-,-(CH) ₂ ) z-, -O (CH ₂ ) _z O-, -O (CH ₂ ) _z- , -OCH _2- C (CH ₃ ) _2- CH ₂ O-, -COO- (CH ₂ ) _z- OCO -Or -OCO- (CH ₂ ) _z- COO-,
z is an integer of 1 to 10 independently of each other.
k is an integer from 1 to 3
n and m are independently integers of 0 to 3. In the above chemical formula 1,
The cross-linking agent compound according to claim 1 or 2, wherein L ₁ and L _{2 are independently alkylene groups having 1 to 5 carbon atoms.} The cross-linking agent compound according to any one of claims 1 to 3, wherein the cross-linking agent compound represented by the chemical formula 1 includes a compound represented by the following chemical formula 1-1.
[Chemical formula 1-1]

In the above chemical formula 1-1,
A'is a divalent aromatic functional group,
L _{4 to} L ₇ are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms.
_{R 3, R 3 ', R} 4, and _{R 4'} are each independently a silicon-containing monovalent functional group. In the above chemical formula 1,
The cross-linking agent compound according to any one of claims 1 to 4, wherein the silicon-containing monovalent functional group is a functional group represented by the following chemical formula 3.
[Chemical formula 3]

In the above chemical formula 3,
R _{5 to} R ₇ are each independently one of hydrogen or an alkyl group having 1 to 10 carbon atoms. The cross-linking agent compound according to any one of claims 1 to 5, which is used for photosensitive material applications. A photosensitive composition comprising the cross-linking agent compound according to any one of claims 1 to 6. A photosensitive composition comprising a cross-linking agent compound represented by the following chemical formula 1; and a polymer containing at least one or more carboxyl groups:
[Chemical formula 1]

In the above chemical formula 1,
A is a monovalent to tetravalent aromatic functional group.
j is an integer of 1 to 4 and
L ₁ and L ₂ are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms.
R ₁ and R ₂ are independent silicon-containing monovalent functional groups. The photosensitive composition according to claim 8, further comprising a compound represented by the following chemical formula 4.
[Chemical formula 4]

In the above chemical formula 4,
A'' is a monovalent to tetravalent functional group.
a is an integer of 1 to 4,
b is an integer from 0 to 3 and
The sum of a and b is 1-4,
L _{8 to} L ₁₁ are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms.
At _{least one of R 21} and R ₂₂ is hydrogen and the rest are silicon-containing monovalent functional groups.
R ₂₃ and R ₂₄ are independent silicon-containing monovalent functional groups. The photosensitive composition according to claim 9, wherein the content of the compound represented by the chemical formula 4 is 0.001 part by weight to 10 parts by weight with respect to 100 parts by weight of the cross-linking agent compound represented by the chemical formula 1. .. The photosensitive composition according to claim 10, further comprising a compound represented by the following chemical formula 5.
[Chemical formula 5]

In the above chemical formula 5,
R _{5 to} R ₇ are each independently one of hydrogen or an alkyl group having 1 to 10 carbon atoms. The polymer containing at least one or more carboxyl groups is
Claims 8 to 11 include a first polyamic acid (co) polymer containing a repeating unit represented by the following chemical formula 6 and a second polyamic acid (co) polymer containing a repeating unit represented by the following chemical formula 7. The photosensitive composition according to any one of the above:
[Chemical formula 6]

[Chemical formula 7]

Among the chemical formula 6 to 7, X ₃ and X ₆ are each independently a tetravalent organic group represented by the following Chemical Formula 8,
[Chemical formula 8]

In the above chemical formula 8,
R _{13 to} R ₁₈ are independently hydrogen or alkyl groups having 1 to 6 carbon atoms.
L'is a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO _2- , -CR ₁₉ R ₂₀ -,-(CH ₂ ) _Z- , -O _{(CH 2) Z O -,} - COO (CH 2) Z OCO -, - CONH-, or any one selected from among phenylene,
R ₁₉ and R ₂₀ are independently hydrogen, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, respectively.
z is an integer from 1 to 10.
Y ₃ is a divalent organic group represented by the following Chemical Formula 9,
[Chemical formula 9]

In the above chemical formula 9,
T is a tetravalent organic group represented by the above chemical formula 8.
D ₁ and D ₂ are independently an alkylene group having 1 to 20 carbon atoms, a heteroalkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. It is one of the heteroarylene groups having 2 to 20 carbon atoms.
Y ₆ is a divalent organic group represented by the following chemical formula 10.
[Chemical formula 10]

In the above chemical formula 10,
A'is a Group 15 element,
R'is hydrogen, or an alkyl having 1 to 10 carbon atoms.
a is an integer from 1 to 3 and
At least one of _{Z 1 to} Z _{4 is nitrogen,}
The rest is carbon. A photosensitive material comprising a cured product of the photosensitive composition according to any one of claims 7 to 12. The photosensitive material according to claim 13, wherein the cured product of the photosensitive composition contains a combination of a cross-linking agent compound represented by the following chemical formula 11 and a polymer containing at least one carboxyl group.
[Chemical formula 11]

In the above chemical formula 11,
A is a monovalent to tetravalent aromatic functional group.
j is an integer of 1 to 4 and
L ₁ and L ₂ are independently one of an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms.